Stable solid disinfectant compositions



hired STABLE SOLID DISINFECTANT CUMPGSITIONS No Drawing. Application January 25, 1957, Serial No. 636,245

9 Claims. (Cl. 167-18) This invention relates to stable, solid disinfectant compositions capable of providing in aqueous solution hypobromite ions or available bromine or a mixture of available chlorine and available bromine.

It has been discovered that aqueous solutions containing hypobromite ions or available bromine possess extraordinary disinfectant properties, particularly against micro-organisms (e. g., M. pyogenes var. aureus) which are difficult to control. However, solid compositions that produce hypobromite ions or available bromine in aqueous solutions, such as exemplified by alkali metal hypobromites, tend to be unstable; similarly, solid mixtures of hypobromites such as sodium hypobromite in combination with hypochlorites tend to be unstable.

We have discovered stable, solid compositions that contain a hypochlorite component in combination with a bromide and which provide hypobromite ions or available bromine in aqueous solution. These solid compositions contain (1) a hypochlorite component that is stable in the solid state and is either (a) anhydrous or (b) has Water of hydration firmly bound thereto to the extent that the bromide compound will not readily pick up that water of hydration, and (2) a bromide compound that is either (a) anhydrous or (b) has water of hydration firmly bound thereto to the extent that the hypochlorite component will not readily pick up that water of hydration.

In our stable solid compositions, the hypochlorite component and bromide compound are each anhydrous with respect to the other in that neither ingredient is capable of yielding water of hydration to the other. The hypochlorite component and bromide do not readily interact by virtue of the ability of the hypochlorite component to .maintain its original degree of hydration in the presence of. the bromide compound. It is understood that by degree of hydration we also include those hypochlorite components which are anhydrous, in which case the degree of hydration is nil. Thus, the hypochlorite component must not readily pick up water from or lend water to the bromide compound, and vice versa; such solid compositions will be stable and the hypochlorite component therein will be capable of substantially maintaining its normal stability. For example, both the hypochlorite component and bromide may be either (a) anhydrous or (b) hydrated, or (c) the hypochlorite component may be hydrated while the bromide compound is anhydrous.

,In the event that both the hypochlorite component and .bromide are hydrated, each of these ingredients must not readily pick up water of hydration from the other. On the other hand, if the bromide compound is anhydrous and the hypochlorite component is hydrated, the bromide compound must not readily pick up that water of hydration.

The term hypochlorite component herein refers to solid compounds or complexes that (1) are stable, (2) provide hypochlorite or available chlorine in aqueous solution, (3) are either (a) anhydrous or (b) have water 2,815,31 1 A Patented Dec. 3, 1957 ice . aqueous solution.

The term bromide or bromide compound herein refers to solid compounds that (1) are substantially neutral to alkaline, (2) provide bromide ions in aqueous solution, but provide hypobromite ions or available bromine in the presence of the hypochlorite component and water, and (3) are either (a) anhydrous or (b) have water of hydration firmly bound thereto to, the extent that the hypochlorite component will not readily pick upv water of hydration from the bromide compound, thus substantially maintaining the normal stability of the hypochlorite component.

The term stable herein refers to the ability of the solid hypochlorite component to retain a substantial portion of its originally available chlorine content, thus substantially maintaining its normal stability, in combination with the bromide compound in dry, closed containers. This requires, as a prerequisite, that the solid hypochlorite component per se be stable and be either anhydrous or,

' if hydrated, have its water of hydration firmly bound thereto. In order to be considered stable, the hypochlorite component, in combination with the bromide, must retain at least 50% of its originally available chloriuev content when stored in a dry, air-tight container (e. g., glass bottles) at F. for six months.

The available chlorine in the hypochlorite component enables the bromide compound to provide hypobromite ions. or available bromine in aqueous solution. One chemical equivalent weight of available chlorine will enable one equivalent weight of bromide ion to provide substantiallyone equivalent weight of available bromine. When the solid composition provides a greater molecular equivalent amount of available chlorine in solution than available bromine, such solutions will provide a mixture of available bromine in combination with available chlorine. Solutions of our solid compositions possess greater germicidal activity than if a molecular equivalent amount of available chlorine-alone were present.

Our invention contemplates the use of stable, solid hypochlorite components that are essentially anhydrous. These components include compounds such as calcium hypochlorite (anhydrous), diand tri-chloroisocyanuric acid, chloromelamine such as disclosed in U. S. Pat. No. 2,184,883, and the like.

In addition, the hypochlorite component may be a stable, solid complex or compoundv having water of hydration firmly bound thereto such as exemplified by chlorarnine, T (i. e., sodium p-toluenesulfonchloramine having three moles of water of hvdrati-on), chloramine B (i. e., sodium bermenesulfonchloramine having two moles of Water ofhydration), calciumhypochlorite (i. e., Ca(OCl) -4H O), a. chlorinated trisodium phosphate containing /24% available chlorine produced by combining trisodium phosphate in its normal Na PO -12H O form and an alkali metal hypochlorite (e. g., sodium hypochlorite) in accordance with the procedures set forth in Mathias Patent No. 1,555,474 and Adler Patent No. 1,965,304, and the like.

When our solid composition contains an anhydrous hypochlorite component, anhydrous alkali metal bromides such as potassium bromide and sodium bromide may be used.

We have found that when alkali metal bromides such as potassium bromide, sodium bromide and sodium bromide dihydrate are admixed with a hypochlorite component having water of hydration. firmly bound thereto,

germicidal activity thereto.

the bromide does not tend to pick up that water of hydration.

Alkaline earth metal bromides such as solid calcium bromide may also be used, but are generally restricted to uses wherein the hardness constituents and turbidity introduced into aqueous solutions by these bromides are not objectionable.

Table I shows some of the (a) anhydrous hypochlorite components and (b) hypochlorites having Water of hydration firmly bound thereto that may be admixed with various bromides in accordance with our invention.

Normally, our solid composition possesses observable disinfectant properties in solution when said composition yields at least about 0.078% by weight available bromine (based on the weight of said solid composition) and at least about 0.5% by weight available chlorine (based on the weight of said solid composition). Our solid composition should not contain more bromide than that which would provide 225% by weight available bromine, based on the weight of available chlorine, in solution; otherwise unreacted bromide would remain as such in the disinfecting solution and would not contribute any beneficial The maximum percent by weight of available chlorine that may be present in our solid composition is determined by the maximum amount of available chlorine that can be yielded by the hypochlorite component when about 0.078% by weight available bromine (based on the weight of the solid composition) is yielded by the solid composition in solution. The

solid disinfectant composition should yield, in solution,

at least about 1% by weight, preferably about 5-20%, available bromine based on the weight of available chlorine. Obviously, if desired, the solid composition may contain suflicient bromide so as to provide in aqueous solution, on a weight basis, more bromide ion than available chlorine.

Table II illustrates the stability of our compositions by showing the results of storage tests on two examples of mixtures of alkali metal bromides and chlorinated trisodium phosphate. These tests were run by storing the described materials in 1-pound, screw-top glass jars at 80 F. for nine months. The available chlorine content is shown initially and periodically for nine months.

TABLE II Percent available chlorine after- Examples ofs u'itable mixtures ofchlo'rinated trisodium phosphate and sodium bromide dihydrate are as follows (all percentages in Examples 1-4 are based on the weight of the solid composition):

Example 1 6.86 gms. NaBr-2H O (6.42% of total) gms. chlorinated trisodium phosphate (3.5% available Cl In solid mix:

3.28% available chlorine 3.44% NaOCl In solution:

0% available chlorine 7.38% available Br 5.49% NaOBr Example 2 NaBr-2H O av. Br av. chlorine NaOCl Example 3 1 gm. NaBr-2H O (.99% of total) 100 gms. chlorinated trisodium phosphate In solid mix:

3.47% available C1 3.65% NaOCl In solution:

2.96% available C1 1.14% av. Br

3.11% NaOCl .85% NaOBr Example 4 1.34 gms. NaBr-2H O (1.32% of total) 100 gms. chlorinated trisodium phosphate In solid mix:

3.46% available C1 3.64% NaOCl In solution:

1.52% av. Br

2.78% av. C1

2.94% NaOCl 1.14% NaOBr In the above examples, the sodium bromide dihydrate may be incorporated in its usual crystalline form, being mixed with crystals of chlorinated trisodium phosphate. In order to avoid separation in packaging, it is preferred that the crystals or particles be of substantially same order of size.

The following examples illustrate suitable mixtures which include, as the hypochlorite component, calcium hypochlorite, chlorarnine T, and chloromelamine. (All of the figures shown in these examples are based on percent by weight of the composition.)

5 Example 8 cates that less than 99.9% of the organisms were de calcium hypochlorite 1 10 stroyeda'where a'figure is shown, it indicates over; 99.9% NaBr 2 destruct on ot the organism. The data set forth in these Trisodium Phosphate 1 88 tables (1. e., ables VrX )j1 ll1 d1CZ1te that solutlons of our 5 solid compositions, containlng a hypochlorrte component x pl 9 and. bromide, possess greater. germicidal-activity than if Chloramine T 99 a molecular equivalent amount of available chlorine NaBr 1 alone were present.

' In Table V the composition tested contained 63% Example 10 10 chlorinated trisodium phosphate (3.5% availableichlochl i T 90 rine), 18% sodium tripolyphosphate, and 19% sodium N B 10 metasilicate pentahydrate. The data shown in Table V, V i as well as Table VI, were obtained using the-Weber and Emmlle 11 Black method (Am. J. Public Health, 38, 1405-1417 Chloramine T 50 with M. pyogenes var..aureus.washed from a 24-hour NaBr 4 agar slant and suspended in sterile tap water; the plating Sodium carbonate 46 medium was tryptone glucose extract .agar, the plates Example 12 being incubated for 24 hours at 37 -C. TableV shows the disinfectant properties'of said composition after ex- Chlofomelaminel 9 20. posure periodsof 15 sec., 30 sec., 60 sec., 120 sec., and N831 1 300 sec. with various levels of available chlorine.

Example 13 In acquiring the data set forth in Table VI, the same product employed in obtaining the data shown .in Table Chloromelamme l 80 V, plus 1.32% NaBr-ZH O, was employed. The data in NaBY Table VI show the disinfectant properties'of said prod- Anhydrous. nct afterexposure periods of 15 sec., sec., 60 sec., Diluents such as cleaning agents and the like may, if 23 32;" ;i gg h "g Same levels of available desired, be included in our compositions as long as those Y diluents do not destroy the stability of our compositions, 30 TABLE V and enable the hypochlorite component to maintain its original degree of hydration. For example, the chlorin- Available t d t i di h h b id mixture may b Chlorine, 15 Sec. 30 Sec. 60 Sec. 120 Sec. 300 Sec. marketed with a considerable amount of other materials such as complex phosphates, silicates, and even coloring materials such as potassium permanganate. 1 'TNTC TNTo 'IN'IO 1 1 Table III shows the results of tests on M. pyogenes TNTO' 'TNTC 400mm 0 0 var. aureus by the Weber and Black method (Am. J. TNTO TNTC 'TNIO 325 13 Public Health, 38, 14051417). TNTC indicates that TNTC TNTO Q 48 2 less than 99.9% of the organisms were destroyed. Where TN'IG TNTC TNTC TNTC 3s a figure is shown, it indicates over 99.9% destruction of TNTO TNTC TNTG TNTC 5 the organism. The germicide was calcium hypochlorite, TNTC TNTO TNTC TNTC TNTC in concentrations which provide the parts per million of TNTO TNTO TNTO TNTC TNTO chlorine indicated. The data shown in Table IV were obtained with calcium hypochlorite plus 20% sodium TABLE bromide when the same test procedure was used.

TABLE III oiii ii g 15 Sec. 30 See. 60 Sec, 120 Sec. 300 Sec.

and/or Bromine, p. p. 111. Available Chlorine, 15 See. 30 Sec. 60 Sec. 120 Sec. 300 Sec. 50

p. p. m.

TNIO 64 o 0 0 19 16 4 0 0 TNTO 3 0 o 0 2 2 0 o 0 TNTC 149 61 0 o 54 12 4 0 0 2s 11 5 0 0 6 3 0 0 o TNTC TNTC TNTO TNTC TNTC TNTO 85 83 17 4 TN'IC TNTC TNTO TNTC TNTO 195 12 9 2 1 TABLE IV The data set forth in Table VII were obtained using the same product employed in obtaining the data shown Available in Table V but employing higher levels of available chlo- Chlorin 15 5% 30 SW 60 5% 120 gem 300 s rine and obtaining -test,data after exposure periods of 1 and/0r Bromine, sec., 5 sec., 10 sec., and 20 sec.

The data set forth in Table VIII were obtained'using the same product (containing 1.32% NaBr'2H O) used 1 3 0 0 0 in acquiring the data shown in Table VI but employing 1 0 0 0 the higher levels of available halogen used in Table VII 0 0 0 0 0 and using exposure periods of 1 sec., 5 sec., 10 sec., and 31% 0 0 0 0 20 sec.

' TNTO TNTC TNTQ 23 1 In Tables VII and VIII, the organism tested was M. 2 13 35 31 5 0 pyogenes var. aureus, but the tests were made by the The following tables show the results of bacteriological studies on various compositions hereof. TNTC indiglass-slide method of C. K. Johns (AJPH, 37, 10-1947). The plates were made with tryptone glucose extract agar; duplicate plates were made-from 200 and pap-m,

concentration of total available halogen. Tests were conducted at 20 C.

The data shown in Table IX were obtained using chlorinated trisodium phosphate. The table shows the elfectiveness of this product using various levels of available chlorine and exposure periods of 15 sec., 30 sec., 60 sec., 120 sec., and 300 sec.

Table X shows test data obtained using the same chlorinated trisodium phosphate product, plus 1.32% NaBr-ZH O, and total amount of available halogen used in obtaining the data shown in Table IX. 7

In Tables IX and X, 2.5 ml. of a suspension of M. pyogenes var. aureus was added to 2.5 ml. of sterile peptone at a concentration of 1000 p. p. m. in sterile testing jars. The Weber and Black test was then performed in the usual manner.

TABLE IX Available 15 Sec. 30 Sec. 60 Sec. 120 Sec. 300 Sec. Chlorine, p. p. m.

1 TNTC TNTC TNIO 120 4 TNTO TN TC TN TO 31 1 TNTC TNTC TNTO TN'IC 1 TNTO 'INTC TNTO TNTC TN'IC TNTC TNIG TNTO 'INIC TN'IC TNTO TNTO TNTO TNTO TNTC TNIO TNTC TNTC 'IN'IO TNTC TNTG TNTC 'INTO TNTC TABLE X Available Chlorine and/or 15 See. 30 Sec. 60 See. 120 Sec. 300 Sec. Bromine, p. p. In.

TN TC TNTC 13 40 1 TN TC 168 4 0 TN TC TN TC 168 34 0 'IN'IO TN TO 29 28 0 This application is a continuation-in-part of Ellis and Dvorkovitz applications Serial Nos. 438,621 and 438,622, filed June 22, 1954, both now abandoned. I

The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art.

We claim:

1. A stable, solid disinfectant composition comprising: a stable, solid, water-soluble hypochlorite component and a substantially neutral to alkaline, solid, water-soluble metal bromide which do not yield water of hydration to each other, thereby permitting the hypochlorite component to maintain its original degree of hydration in said composition; said hypochlorite component and said bromide being present in said composition in proportions that provide, in solution, at least about 1% by weight available bromine based on the Weight of available chlorine; and said composition being sufliciently stable to permit said hypochlorite component to retain at least 50% of its originally available chlorine content when stored in a dry, air-tight container at 80 F. for six months.

2. The composition of claim 1 wherein the bromide is an alkali metal bromide.

3. A stable, solid disinfectant composition comprising: a stable, solid, water-soluble hypochlorite component and a substantially neutral to alkaline, solid, water-soluble metal bromide which do not yield water of hydration to each other, thereby permitting the hypochlorite component to maintain its original degree of hydration in said composition; said hypochlorite component and said bromide being present in said composition in proportions that provide, in solution, more hypochlorite ions than equivalent amount of hypobromite ions; said solid composition providing at least about 0.5% available chlorine based on the Weight of said solid composition and at least about 0.078% available bromine based on the weight of said solid composition; and said composition being sufliciently stable to permit said hypochlorite component to retain at least 50% of its originally available chlorine content when stored in a dry, air-tight container at F. for six months.

4. A stable, solid disinfectant composition comprising: a stable, solid, Water-soluble hypochlorite component and a substantially neutral to alkaline, solid, water-soluble metal bromide which do not yield water of hydration to each other, thereby permitting the hypochlorite component to maintain its original degree of hydration in said composition; said hypochlorite component and said bromide being present in said composition in proportions that provide at least about 0.5% available chlorine based on the weight of said solid composition and at least about 0.078% available bromine based on the weight of said solid composition; and said composition being sufficiently stable to permit said hypochlorite component to retain at least 50% of its originally available chlorine content when stored in a dry, air-tight container atv 80 F. for six months.

5. The composition of claim 4 wherein the hypochlorite component is calcium hypochlorite and the bromide is an alkali metal bromide.

6. The composition of claim 4 wherein the hypochlorite component is a polychloroisocyanuric acid and the bromide is an alkali metal bromide.

7. The composition of claim 4 wherein the hypochlorite component is chloromelamine and the bromide is an alkali metal bromide.

8. The composition of claim 4 wherein the hypochlorite component comprises an aryl monocarbocyclic group having six carbons in the ring with a substituent bonded to said ring and water of hydration, and the bromide is an alkali metal bromide.

9. A stable, solid disinfectant composition comprising: chlorinated trisodium phosphate having at least /2% available chlorine and a water-soluble metal bromide which do not yield Water of hydration to each other, thereby permitting the chlorinated trisodium phosphate to maintain its original degree of hydration in said com- References Cited in the file of this patent UNITED STATES PATENTS 1,555,474 Mathias Sept. 29, 1925 '1 Salerni July 29, 1941 Kitter Aug. 7, 1945 Smith Jan. 29, 1946 Block et al Feb. 8, 1949 FOREIGN PATENTS Great Britain Sept. 22, 1910 OTHER REFERENCES McCullock: Disinfection and Sterilization, 2nd ed., 1945, pp. 327-330. 

1. A STABLE, SOLID DISINFECTANT COMPRISING: A STABLE, SOLID, WATER-SOLUBLE HYPOCHLORITE COMPONENT AND A SUBSTANTIALLY NEUTRAL TO ALKALINE, SOLID, WATER-SOLUBLE METAL BROMIDE WHICH DO NOT YIELD WATER OF HYDRATION TO EACH OTHER, THEREBY PERMITTING THE HYPOCHLORITE COMPONENT TO MAINTAIN ITS ORIGINAL DEGREE OF HYDRATION IN SAID COMPOSITION; SAID HYPOCHLORITE COMPONENT AND SAID BROMIDE BEING PRESENT IN SAID COMPOSITION IN PROPORTIONS THATT PROVIDE, IN SOLUTION, AT LEAST ABOUT 1% BY WEIGHT AVAILABLE BROMINE BASED ON THE WEIGHT OF AVAIBLE CHLORINE; AND SAID COMPOSITION BEING SUFFICIENTLY STABLE TO PERMIT SAID HYPOCHLORITE COMPONENT TO RETAIN AT LEAST 50% OF ITS ORIGINALLY AVAILABLE CHLORINE CONTENT WHEN STORED IN A DRY AIR-TIGHT CONTAINER AT 80*F. FOR SIX MONTHS. 